JPS61225139A - Clathration separation using supercritical or pressure-liquefied gas as medium - Google Patents

Abstract

PURPOSE:Utilizing the phenoma that clathrates are selectively and reversibly formed and dissociated in a supercritical or pressure liquefied gas, and allowing an entrainer to coexist, the objective substance is obtained from a mixture in high purity and high yield. CONSTITUTION:An extraction phase is obtained from a mixture using, as a solvent, a supercritical gas or high-pressure liquefied gas such as carbon dioxide or nitrous oxide and the gas is used as a medium to effect the reaction between the clathrate lattice component such as urea or deoxycholic acid and the solute in the extraction phase to form and dissociate the clathrates selectively and reversibly whereby the extraction phase containing the desired solute is collected. Then, the gas as the solvent is removed to give the objective compound. In case that the gas are a little weak in capability of forming clathrates, an entrainer stimulating clathrate formation such as methanol is admixed. The ability of the gas as a solvent is heavily dependent on the pressure and the separation of gas from the desired compound is rapidly carried out by pressure reduction.

Description

Detailed Description of the Invention "Field of Application in Industry-1-" The present invention utilizes the selective and reversible formation and decomposition of certain clathrate compounds in supercritical gas or high-pressure liquefied gas. The present invention relates to a method for separating a target component from a mixture with high purity and high yield.

``Prior art'' Separation methods that utilize the selective formation of clathrate compounds have been widely used in laboratories; It is difficult to efficiently isolate mixtures. For example, separation of mixtures rich in highly unsaturated fatty acids from natural oils and fats using the urea fractionation method has been carried out industrially, but it is considered difficult to convert them into constituent components. ing.

In other words, as the inclusion operation is repeated, the difference in the stability of the inclusion compounds of the components in the adduct or non-adduct becomes gradually smaller, and not only does efficient separation become impossible, but also It cannot be avoided that the inclusion operation each time is extremely complicated. For example, in a urea fractionation method using a urea-saturated methanol solution, adducts are crystallized and filtered out in one operation, and non-adducts are separated and concentrated from the filtrate using methanol and filtrate. Removal of dissolved urea is required. In addition, a method has been proposed in which unsaturated fatty acids are separated using solid urea as an inclusion lattice component and aliphatic hydrocarbons or alicyclic hydrocarbons as solvents (Japanese Patent Application Laid-Open No. 164196/1982), but crystallization and Although the step of removing urea from the filtrate is omitted, it is still complicated to perform multiple operations in industrial Ichikawa and Momo.

On the other hand, supercritical gas extraction (Special Publication No. 54-10539)
is also known, but its performance in separating components with similar structures is low;
The problem is that the practical range is limited.

``Problems to be Solved by the Invention'' Here, the present inventors have discovered that the clathrate compounds contain components that differ in their stability.

As a result of various studies on how to efficiently separate desired components, the following invention was finally completed.

``F-stage to solve the problem'' In other words, the invention involves obtaining an extraction phase from a mixture using a supercritical gas or high-pressure liquefied gas as a solvent, and using the gas in such a state as a medium to prevent the formation of clathrate compounds. When the degree of activation is low, an entrainer having the ability to activate inclusion formation is made to coexist with the entrainer, pressure and temperature are used as operating factors, and the inclusion lattice component is reacted with the solute component in the extraction phase. A supercritical gas or Inclusion separation using high pressure liquefied gas as a medium
: We aim to provide the following.

Selectivity in the formation of clathrate compounds is exerted by the shape of the gaps specific to the crystal structure of the host molecule, which is an inclusion lattice component. This crystal structure may be newly formed due to the presence of a guest molecule incorporated into the inclusion lattice, or may exist stably regardless of the guest molecule. A typical example of the former is urea, and a typical example of the latter is zeolite, an adsorbent with shape selectivity. Also,
The conditions for the formation of clathrate compounds to be reversible are as follows:
The interaction between the host molecule and the guest molecule is a physical bond 1, for example, the van der Waal
s) It is preferable to use forces, hydrogen bonds, etc. Table 1 shows the generally known host-guest molecule relationships.

Now, regarding the formation and decomposition of clathrate compounds.

In order to increase the selectivity and reversibility of the bond between the host and GesI molecules according to the purpose, the selection of the solvent is particularly important. By using a supercritical gas or high-pressure liquefied gas that has a high temperature, has an affinity with the mixture to be fractionated, and has an effect as an activator for the inclusion reaction, it is possible to achieve high temperatures that were previously impossible. This enabled separation with high purity and high yield. That is, it has been discovered that supercritical gas or high-pressure liquefied gas near the critical point has low viscosity and high permeability, and these properties work advantageously for the formation of clathrate compounds, which are heterophasic reactions.

However, in exceptional cases where certain types of supercritical gases or high-pressure liquefied gases activate the formation of clathrate compounds to a particularly low degree, the clathrate reaction will not proceed smoothly; It has also been found that if a relatively small amount of an entrainer having the ability to activate clathrate formation is co-present, the activation of clathrate formation can be promoted.

The equilibrium reaction of clathrate formation sensitively follows temperature, which is a controlling factor, in the supercritical gas or high-pressure liquefied gas phase.
The R temperature can shift the direction-equilibrium from inclusion formation to decomposition in a relatively short time. At this time, the solvent capacity of supercritical gas or high-pressure liquefied gas is highly dependent on pressure, so by selecting an appropriate pressure, sufficient solvent capacity can be maintained in the temperature range from clathration formation to decomposition. .

Based on the above two points, as shown in the examples of the present invention, it is possible to concentrate and recover the ('' component) using an extremely simple Qt device and method.

Note that the solvent is not limited to pure components, and the direction of resolution can be determined by changing the composition of the mixed solvent. The inclusion lattice component is not limited to one type, and a combination of multiple types may be used, especially when it is necessary to increase the separation ability of the target component.

According to the method of the present invention, the separation of the target component and the solvent is carried out quickly due to a decrease in pressure, and very little solvent remains in the product, making it possible to recover it almost completely.
Moreover, it has the great advantage of being much more energy efficient than conventional separation methods such as distillation.

Furthermore, the dissolution of the clathrate lattice components into the supercritical gas or high-pressure liquefied gas phase is extremely small and can be ignored, and the guest components in the clathrate compound are quickly entrained in the solvent gas after decomposition. An advantage is that the lattice components can be used repeatedly as they are.

Furthermore, it is also possible to combine the method of the present invention with a reflux method that takes advantage of the difference in solvent capacity due to changes in the temperature and pressure of supercritical gas or high-pressure liquefied gas. It is also possible to use the membrane filtration method or the reverse osmosis removal method in combination, and in this case, the pressure of the system can be used as is as the driving force for separation, making this a very advantageous combination.

In the present invention, carbon dioxide and nitrous oxide are used as supercritical gases or high-pressure liquefied gases, and urea and nitrous oxide are used as inclusion lattice components.
Although a specific example of clathrate separation using deoxycholic acid and methanol as an entrainer and targeting fatty acids and fatty acid esters as mixture components is shown, the present invention is not limited thereto. The inventive idea can be applied to a wide range of combinations.

In inclusion separation, by appropriately adjusting the temperature and pressure in the system, an extraction phase consisting of the desired solute components can be obtained over time under the flow of supercritical gas or high-pressure liquefied gas, but the target components and A conceptual diagram of concentration separation of other constituent components is shown in FIG. Here, a case where the target component forms the most unstable clathrate compound is taken as an example.

During the process, supercritical gas or high-pressure liquefied gas and lattice components are brought into self-flow contact, and a temperature gradient is provided in the recovery section below the column where the contact occurs, so that most of the clathrate compounds are decomposed at the bottom of the column. The upper concentration section has a sufficient length and set temperature so that only the target component is present in the extraction phase at the top of the column.

Side cuts are taken at the point where the concentration of each component is maximum. In this case, the first side cut position from the -4 direction is installed in consideration of the pinch point of the target component, so that the target component can be obtained with a high recovery rate.

The lattice components and supercritical gas or high pressure liquefied gas can be recycled and reused. In addition, the contact method of the tower is
A moving bed, a multistage fluidized bed, a pseudo moving bed, etc. can be selected as appropriate.

EXAMPLES Hereinafter, the present invention will be specifically explained using Examples.

"Example 1" To 16.0 g of fatty acid methyl ester obtained from fish oil, supercritical carbon dioxide at 40'01100 kg/cf G was used as a solvent, and 104.7 g of urea pulverized in a mortar was used as an inclusion lattice component. One separation was performed using The separation device shown in FIG. 2 was used.

First, predetermined amounts of raw materials and clathrate lattice components are charged into the raw material tank 5 and the clathrate compound forming tank 6, respectively, the constant temperature tank 10 and pressure holding valve 11 are adjusted to predetermined temperatures and pressures, and the high-pressure pump 3 is activated. After the system reaches a predetermined pressure, the pressure reducing valve 7 is opened and the flow of supercritical gas is started. The pressurized carbon dioxide is in a critical gas state, dissolves soluble components in the raw material in the raw material tank 5, and is introduced into the clathrate compound formation tank 6. A part of the entrained solute component forms an clathrate compound with the inclusion lattice component in the tank 6, is separated from the extraction phase, and remains in the tank 6. The remainder is entrained by the supercritical gas and flows out from the tank 6. The formation of clathrate compounds differs depending on the types of inclusion lattice components (host molecules), solute components (guest molecules), and gases (solvent), as described above, and this leads to The solute components in the supercritical gas are fractionated.The extraction phase flowing out from the tank 6 is passed through the pressure reducing valve 7.
After the pressure is reduced and the solute is released into the collector 8, the flow rate is measured by a gas meter 9. In addition, the solute trapped in the collector 8 was sampled as appropriate, and the weight was 1.111.
and conduct compositional analysis.

Since this separation device is of a semi-batch type, the solute concentration in the clathrate compound forming tank 6 changes over time and becomes zero when all the soluble components in the raw material tank 5 are extracted.

Furthermore, if the supercritical gas continues to flow as a solvent, the unstable clathrate in the tank 6 will decompose, and eventually the solute will hardly flow out of the tank 6. At this point, the clathrate in tank 6 is stable, and in order to further rapidly decompose it, it is necessary to shift the clathrate equilibrium.

Methods for this include increasing the solubility of guest molecules in the extraction phase by increasing the pressure or changing the type or composition of the solvent, destabilizing the clathrate by increasing the temperature, and solubilizing the inclusion lattice component in the extraction phase. Furthermore, combinations of these methods are possible. In other words, the selection of the decomposition method should take into consideration operability and efficiency such as selective recovery of guest molecules, recovery of inclusion lattice components, and decomposition rate, but the most common method is , decomposition accompanied by temperature raising operation. Therefore, the decomposition of the clathrate compound is carried out by increasing the pressure and temperature in the system while keeping the gas flowing. In addition, l is a gas cylinder, 2 is a cooler,
4 is a heater.

The results are shown in Table 2 and FIGS. 3 and 4, where the outflow rate refers to the outflow ratio with respect to the total outflow amount (8, 4 g).

The separation performance of fatty acid methyl esters having 20 carbon atoms (hereinafter abbreviated as C20) and 22 carbon atoms (hereinafter abbreviated as C22) in fish oil was examined.

Fatty acid methyl esters with few double bonds form stable clathrate compounds in supercritical carbon dioxide, and in the entire outflow area, the effluent contains mostly eicosapentaenoic acid (hereinafter abbreviated as EPA or C20-s). ), methyl ester of docosahexaenoic acid (hereinafter abbreviated as DHA or C22-6). Here, in the examples of the present invention, Cm-n represents a fatty acid or a derivative thereof having m carbon atoms and n double bonds. Note that the large change in the composition ratio in the effluent near the final flow rate is due to the slight difference in separation performance due to the difference in the number of double bonds due to the fact that this device is a semi-batch type. This is probably due to the fact that it was expanded.

(1)) For mixtures with the same prime number and a large difference in the number of double bonds, if the recovery operation by decomposition of the clathrate compound is used in conjunction with the recovery operation, it is possible to achieve a high recovery rate and high purity separation method with an extremely simple operation. It is simple and industrially applicable.

In addition, in the supercritical gas extraction method carried out for comparison, the composition ratio in the effluent is almost the same as the composition ratio in the charged raw material until near the final turnover rate, and the separation performance is low.

Table 2 C20 due to the difference in the number of double bonds in the effluent.
Composition of C22 Fatty Acid Methyl Ester "Example 2" Ethyl ester mixtures of C1B fatty acids each having one double bond number as shown in Table 3 were separated in the same manner as in Example 1. 7.0 g of the raw material mixture and 101 g of urea pulverized with a vibrating ball mill were used. The total flow rate was 2.5 g, which is 36% of the raw material. When almost no effluent was obtained, the clathrate was taken out of the system and decomposed using hot water, yielding 4.3 g of clathrate decomposition product. Table 3 and FIG. 5 show the compositions of the effluent and clathrate decomposition products.

The more double bonds there are, the higher the concentration ratio to the raw material composition, and by repeating the same operation on the effluent,
It can be seen that separation of each component is possible.

The phenomenon in which the composition of components with a large number of double bonds decreases with the outflow rate is due to the fact that the lattice components are not updated, and is not a wood-related problem.

In the supercritical gas extraction method used for comparison, it is almost impossible to separate mixtures that have the same number of carbon atoms but differ in number of double bonds by one.

Table 3 Composition of fatty acid methyl ester of C1θ according to the difference in the number of double bonds in the effluent "Example 3" Using the separation apparatus shown in FIG. .6 g of urea and 113.5 g of urea pulverized with a vibrating ball mill were used, and carbon trioxide was used at 0.3 m/min at 20°C, and 3 m/min when the temperature was raised. The amount of effluent collected by the separator 8 was 9.6 g, which was about 91% of the raw material.

Table 4 as well as FIG. 6 show the compositional changes in the effluent of the main components in the methyl esters of fatty acids obtained from fish oil.

After 1 hour, the clathrate compound was formed in high-pressure liquefied carbon dioxide at 1100 kg/cm"G of 20'O, and then, when almost no ejected material was obtained under this condition, the pressure was increased to 200 kgldG, and further. The clathrate compound was decomposed by gradually increasing the temperature to 80°C.

It is generally known that urea clathrate compounds of fatty acids and their derivatives become more unstable as the number of carbon atoms decreases and as the number of double bonds increases.
The behavior in the supercritical carbon dioxide phase is similar. That is, EPA and DHA, which are highly unsaturated fatty acids, do not stably form clathrate compounds with urea, and most of them flow out together with carbon dioxide during formation of clathrate compounds. In addition, the EPA, D
It can be seen that HA clathrate compounds are rapidly decomposed at considerably low temperatures. On the other hand, saturated fatty acids and unsaturated fatty acids with few double bonds form stable clathrate compounds with urea, and when clathrate compounds are formed, the composition ratio in the effluent is smaller than that in the raw material composition, and most of the clathrates are As they decompose, they flow out, depending on their stability and concentration. Since this example is a semi-batch type, the inlet composition of the clathrate compound forming tank 6 changes over time and the clathrate lattice components are not updated, so the outflow composition changes in a seemingly complicated manner.
The separation due to the difference in stability can be understood by comparing the composition of the effluent from the formation and decomposition of the clathrate compound and the composition of the raw material.

Table 4 Changes in effluent composition of fatty acid methyl ester main components obtained from fish oil "Example 4" Using the separation apparatus shown in Figure 2, for 10.2 g of fatty acid ethyl ester obtained from the raw material evening primrose seed oil, Urea 1 pulverized by a vibrating ball mill is placed in the clathrate formation tank 6.
When the clathrate compound was formed at a carbon dioxide pressure of 100 kg/dG and a temperature of 25°C,
．． 9 g of effluent was obtained. After the formation of the clathrate compound, the pressure inside the system is reduced to atmospheric pressure, and the urea adduct in the tank 6 is taken out.
When dissolved in hot water, 5.3 g of clathrate decomposition product was obtained.

Evening primrose seed oil contains γ-lylunic acid (
CI8-3) is included at about 8%, but 1 of the double bonds
Since it contains a large amount of linoleic acid (CIll-2), its concentration becomes extremely complicated using the usual urea addition method.

However, according to this example, as shown in Table 5, γ-lylunic acid in the total effluent was concentrated to about twice the average composition in one simple operation, and the γ-lylunic acid in the clathrate formed , the raw material composition ratio has decreased to about one-third. On the other hand, since linoleic acid is contained in the clathrate decomposition product at a considerable concentration, it is understood that it is possible to concentrate γ-linolenic acid to a high degree of purity by repeating this operation.

"Example 5" A fatty acid mixture having the composition shown in Table 6 was prepared and separated in the same manner as in Example 1. Carbon dioxide was used as the supercritical gas, and the temperature was 40'O1 and the pressure was 150 kg/C1'G. As the inclusion lattice component, 95.3 g of urea pulverized with a vibrating ball mill was used.

Changes in the effluent composition of saturated fatty acids and C1a fatty acids are shown in Table 6 and FIGS. 7 and 8.

Regarding these, an attempt was made to compare the separation performance with the supercritical gas extraction method, and it was found that the present example was superior.

That is, in this example, during inclusion formation, the composition of each saturated fatty acid in the effluent was approximately 2% or less, indicating that the separation was extremely good. Further, in the supercritical gas extraction method, it is extremely difficult to separate components having the same number of carbon atoms, but in the present invention, great separation performance can be obtained just by the difference in double bonds.

5.8g of the raw fatty acids formed clathrate compounds, but
Decomposition was performed according to the temperature and pressure increase patterns shown in Table 7 and FIG. Here, the degree of pressure increase is the final temperature of 90'O
It was also determined that supercritical carbon dioxide has sufficient dissolving power for fatty acids. Table 8 and FIG. 10 show changes in the composition of saturated fatty acids flowing out, and it can be seen that fatty acids flow out in descending order of carbon number. Table 9 as well as FIGS. 11 and 12 show differences in outflow composition changes due to differences in the double bonds of C1[1 and C22 fatty acids, respectively.

From these results, it can be seen that there is a clear difference in the number of double bonds during the decomposition of the clathrate compound, and the greater the degree of unsaturation, the easier it is to decompose.

Table 7 Temperature and pressure increase pattern "Example 6" 1.02 g of methanol, which is a good solvent for urea, was added in advance to 5.02 g of fatty acid methyl ester obtained from fish oil with the same composition as used in Example 1 as an entrainer. In addition, pulverized urea as an inclusion lattice component], 02,
2 g of nitrous oxide at 20°O, 100 kg/i
Separation was performed in the presence of methanol as a solvent in a high-pressure liquefied gas state of G. The temperature and pressure increase patterns are shown in Table 10 and Figure 13.
The results are shown in Tables 11 and 12, as well as Figures 14 and 15. Unlike the case in which methanol is not added, which will be described later, the formation of clathrate compounds is clearly observed, and even in supercritical or high-pressure liquefied gas, methanol does not form with urea. It can be seen that it has the ability to activate the formation of adducts.

For comparison, nitrous oxide at 20°C 1l OOkg/d
An attempt was made to separate the same fatty acid methyl ester raw material as in this example using the supercritical gas extraction method using G as a solvent in a high-pressure liquefied gas state, but due to the large dissolving power, the amount extracted gradually decreased over time, and the extraction The composition matched the raw material composition within the analytical error range, regardless of the extraction rate. Furthermore, using urea as an inclusion lattice component did not change the results. In other words, no clathrate formation occurred. Therefore, it is understood that not only the selection of the inclusion lattice components but also the type of gas and the selection of the entrainer are important factors as necessary conditions for the formation of clathrate compounds.

Table 10 Temperature and pressure increase pattern “Example 7” Using the separation apparatus shown in FIG. 2, f! ! A separation experiment was conducted by filling 70 g of deoxycholic acid into the clathrate compound forming tank 6 with respect to 4.5 g of fatty acid methyl ester obtained from oil and using nitrous oxide as a solvent.

When the reaction was carried out at a pressure of 100 kg/cr'G and a temperature of 20° C., 2.6 g of effluent, which is 58% of the raw material, was obtained. Thereafter, as shown in Table 13 and Figure 16, the pressure was increased to 200 kg/dG and the temperature was gradually raised to 90°C, yielding 1.2 g of clathrate decomposition products, with an overall efflux rate of 84%. became. The results are shown in Tables 14 and 15, as well as FIGS. 17 and 18. In this case, unlike Example 6, the clathrate compound was formed without the need for an entrainer, but deoxycholic acid has a high selectivity for the formation of clathrate compounds for the separation of fatty acid methyl esters, whereas urea has a high selectivity for the formation of clathrate compounds. It turns out that there isn't.

Table 13 Temperature and pressure increase pattern "Effects of the invention" The inclusion separation method of the present invention can be applied to all mixtures to be separated in which an appropriate supercritical gas or high-pressure liquefied gas and an inclusion lattice component are found. In particular, this feature can be applied to objects that cannot be separated at high temperatures, such as foods and pharmaceuticals, since they can be operated at around room temperature.
and separation of azeotropic mixtures, which require a large amount of energy and complicated operations. Also,
The present invention is also expected to be applied to the field of analytical chemistry as supercritical chromatography.

[Brief explanation of drawings]

Figure 1 is a conceptual diagram of the continuous separation process according to the method of the present invention, Figure 2 is a conceptual diagram of the semi-batch type separation apparatus used in the examples, and Figure 3 is a conceptual diagram of the semi-batch type separation apparatus used in the examples.
The figure is a graph showing the composition of C20 fatty acid methyl ester depending on the difference in the number of double bonds in the effluent, and Figure 4 shows the composition of C22 fatty acid methyl ester depending on the difference in the number of double bonds in the effluent. The graph shown in Figure 5 shows the difference in the number of double bonds in the effluent of C+a fatty acids.
Figure 6 is a graph showing the composition of ethyl esters, Figure 6 is a graph showing changes in the composition of the effluent mainly composed of fatty acid methyl esters obtained from fish oil, and Figure 7 is a graph showing the composition of saturated fatty acids.
□Graphic diagram showing the composition of the effluent during contact formation, Figure 8 is C
A graph showing the composition of the effluent during inclusion formation of Ill fatty acids, Fig. 9 is a graph showing the temperature increase and pressure increase pattern, Fig. 1
Figure O is a graph showing the composition of the effluent when the clathrate compounds of saturated fatty acids are decomposed, Figure 11 is a graph showing the composition of the effluent when the clathrate compounds of Cra fatty acids are decomposed, and Figure 12 is a graph showing the composition of the effluent when the clathrate compounds of Cra fatty acids are decomposed.
The figure is a graph showing the outflow composition during the decomposition of clathrate compounds of C22 fatty acids, Figure 13 is a graph showing the temperature increase and pressure increase pattern, and Figure 14 is a saturated fatty acid and an unsaturated fatty acid with one double bond. A graph showing the composition of the effluent during inclusion formation and decomposition of methyl esters. Figure 15 is a graph showing the composition of the effluent during the inclusion and decomposition of highly unsaturated fatty acid methyl esters having two or more double bonds. Figure 16 is a graph showing the temperature and pressure increase patterns, Figure 17 is a graph showing the effluent composition of fatty acid methyl esters having saturated and one double bond, and Figure 18 is a graph showing the two measuring instruments 1- FIG. 2 is a graph showing the composition of the effluent of highly unsaturated fatty acid methyl esters. Patent applicant Tadashi Saito 1 outsider 3. 11111:1), i (Fig. 2-Tsubaki 11 marks C τ Yuoku ＾ How many plants W wide me @ Old - 9-0 Flame dψ dimension - Ichishiro Hakubun 9 colors 80%uuuu Poro W 憾(r ・(−■ Gi breeding! Mosquito〈♂ ; 1S Shisa ○〈×mouth4me■ Fence −0
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Claims (5)

[Claims] (1) Obtain an extraction phase from the mixture using supercritical gas or high-pressure liquefied gas as a solvent, and use the gas in such a state as a medium.
If the gas has a low degree of activating the formation of clathrate compounds, an entrainer capable of activating clathrate formation should be added to the gas, and the clathrate lattice components and extraction phase should be controlled by using pressure and temperature as operating factors. By selectively and reversibly forming and decomposing clathrates with solute components in Inclusion separation method using supercritical gas or high-pressure liquefied gas as a medium to obtain components. (2) The clathrate separation method using supercritical gas or high-pressure liquefied gas as a medium according to claim 1, wherein the solvent is carbon dioxide or nitrous oxide. (3) The inclusion separation method using supercritical gas or high-pressure liquefied gas as a medium according to claim 1, wherein the inclusion lattice component is urea or deoxycholic acid. (4) The clathrate separation method using supercritical gas or high-pressure liquefied gas as a medium according to claim 1, wherein the mixture component is a fatty acid or a fatty acid ester. (5) The inclusion separation method using supercritical gas or high-pressure liquefied gas as a medium according to claim 1, wherein the entrainer is methanol when the solvent is nitrous oxide and the inclusion lattice component is urea.